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101.
A series of diazides of 1,2-diphenylacetylenes was photolyzed in matrices at low temperature and transient photoproducts were characterized by using IR, UV/vis methods combined with ESR studies. Theoretical calculations were also used to understand the experimental findings. The introduction of phenylethynyl groups on phenyl azides has little effect on the photochemical pathway. Thus, upon photoexcitation, (phenylethynyl)phenyl azides afforded the corresponding triplet nitrene, which is in photoequilibrium with the corresponding azacycloheptatetraene. In marked contrast, azidophenylethynyl groups exhibited a dramatic effect not only on the photochemical pathway of phenyl azides but also on the electronic and molecular structure of the photoproducts. The patterns of the effect depended upon the relative position of azide groups in the diphenylacetylene unit. Whenever two azide groups were situated in a conjugating position with respect to each other, as in p,p'-, o,o'-, and p,o'-bis(azides), the azides always resulted in the formation of a quinoidal diimine diradical in which unpaired electrons were extensively delocalizedin the pi-conjugation. The situation changed rather dramatically when azide groups were introduced in the meta position. Thus, the formation of azacycloheptatetraene was noted in the photolysis of the m.m'-isomer. ESR studies indicated the generation of a quintet state that was shown to be a thermally populated state with a very small energy gap of ca. 100 cal mol(-1). The m,p'-isomer was shown to be an excellent precursor for the high-spin quintet dinitrene. The IR spectra of the photoproduct showed no bands ascribable to azacycloheptatetraene. The observed spectra were in good agreement with that calculated for the quintet state. Strong EPR signals assignable to the quintet state were observed, along with rather weak signals due to mononitrenes. Moreover, the quintet bis(nitrene) was rather photostable under these conditions. 相似文献
102.
The crystal structure of [{O=VV(salen)}2(mu-F)][VIVO(salen)][BF4].(CH2Cl2)x revealed a hollow cavity with a diameter of 5.3 A that penetrates through the crystal, and a remarkable cyclic chain of the [VO(salen)] unit, a motif that has never been fashioned from oxometal building blocks. These features endow the crystal with a molecular sievelike property for the rapid, reversible, and size-selective absorption of guest CH2Cl2 molecules. 相似文献
103.
Nishimura S Matsunaga S Shibazaki M Suzuki K Furihata K van Soest RW Fusetani N 《Organic letters》2003,5(13):2255-2257
Massadine, a highly oxygenated alkaloid, was isolated from the marine sponge Stylissa aff. massa as an inhibitor of geranylgeranyltransferase type I (GGTase I). The structure of massadine has been deduced from spectral data. Massidine inhibited GGTase I from Candida albicans with an IC(50) value of 3.9 microM. [structure: see text] 相似文献
104.
Yasuhara T Nishimura K Yamashita M Fukuyama N Yamada K Muraoka O Tomioka K 《Organic letters》2003,5(7):1123-1126
[reaction: see text] An omega-nitro-alpha,beta,psi,omega-unsaturated ester underwent a chemoselective conjugate addition of a nitroolefin moiety with aryllithium to produce a psi-aryl-omega-nitro-alpha,beta-unsaturated ester, which was then stereoselectively cyclized by intramolecular nitro-Michael reaction giving a functionalized cyclohexane applicable to the total synthesis of (+/-)-alpha- and beta-lycoranes. 相似文献
105.
Kenichi Futamura 《Annals of Operations Research》2000,93(1-4):71-90
Traditionally, studies on tandem queueing networks concentrate on systems with infinite buffers, exponential service times, and/or single servers where solutions are more tractable. Less research can be found on more general, less tractable systems. We examine multipleserver systems with finite buffers and nonexponential service times, studying the effects of coefficient of variation (cv) of the servicetime distribution on the throughput of these systems, where cv differs among stations.Starting with the single station, we examine the effects of cv and the number of servers at the station on the distribution of interdeparture times. This insight helps explain the differences in throughput seen in the single (fast) server vs. multiple (slow) server problem. These results, in turn, shed light on the server allocation problem when cv differs among stations. We present some observations, as well as the intuition behind them. 相似文献
106.
Kise T Ogasawara T Ashida M Tomioka Y Tokura Y Kuwata-Gonokami M 《Physical review letters》2000,84(9):1986-1989
We propose a measurement setup for detecting quantum noise over a wide frequency range using inelastic transitions in a tunable two-level system as a detector. The frequency-resolving detector consists of a double quantum dot which is capacitively coupled to the leads of a nearby mesoscopic conductor. The inelastic current through the double quantum dot is calculated in response to equilibrium and nonequilibrium current fluctuations in the nearby conductor, including zero-point fluctuations at very low temperatures. As a specific example, the fluctuations across a quantum point contact are discussed. 相似文献
107.
Ignition enhancement by addition of NO and NO2 from a N2/O2 plasma torch in a supersonic flow 总被引:1,自引:0,他引:1
Kenichi Takita Naoyuki Abe Goro Masuya Yiguang Ju 《Proceedings of the Combustion Institute》2007,31(2):2489-2496
The effects of NO and NO2 produced by using a plasma jet (PJ) of a N2/O2 mixture on ignition of hydrogen, methane, and ethylene in a supersonic airflow were experimentally and numerically investigated. Numerical analysis of ignition delay time showed that the addition of a small amount of NO or NO2 drastically reduced ignition delay times of hydrogen and hydrocarbon fuels at a relatively low initial temperature. In particular, NO and NO2 were more effective than O radicals for ignition of a CH4/air mixture at 1200 K or lower. These ignition enhancement effects were examined by including the low temperature chemistry. Ignition tests by a N2/O2 PJ in a supersonic flow (M = 1.7) for using hydrogen, methane, and ethylene injected downstream of the PJ were conducted. The results showed that the ignitability of the N2/O2 PJ is affected by the composition of the feedstock and that pure O2 is not the optimum condition for downstream fuel injection. This result of ignition tests with downstream fuel injection demonstrated a significant difference in ignition characteristics of the PJ from the ignition tests with upstream fuel injection. 相似文献
108.
Shin‐Ichi Yusa Shigeki Awa Masanori Ito Takeshi Kawase Tadao Takada Kenichi Nakashima Dian Liu Shigeru Yamago Yotaro Morishima 《Journal of polymer science. Part A, Polymer chemistry》2011,49(13):2761-2770
Water‐soluble diblock copolymer, poly(N‐isopropylacrylamide)‐block‐poly(N‐vinyl‐2‐pyrroridone) (PNIPAMm‐b‐PNVPn), was found to associate with fullerene (C60), and thus C60 can be solubilized in water. The 63C60/PNIPAMm‐b‐PNVPn micelle formed a core‐shell micelle‐like aggregate comprising a C60/PNVP hydrophobic core and a thermoresponsive PNIPAM shell. The C60‐containing polymer micelle formation and its thermoresponsive behavior were characterized using light scattering and 1H NMR techniques. The hydrodynamic radius (Rh) of the C60‐bound polymer micelle increased with increasing temperature, which was ascribed to the hydrophobic association between dehydrated PNIPAM shells above lower critical solution temperature (LCST). 1H NMR data suggest that the motion of the PNIPAM block is restricted above LCST due to the dehydration of the PNIPAM shell in water. The generation of singlet oxygen by photosensitization by the C60‐bound polymer micelle was confirmed from photooxidation of 9,10‐anthracenedipropionic acid. Furthermore, DNA was found to be cleaved by visible light irradiation in the presence of the C60‐bound polymer micelle. Therefore, there may be a hope for a pharmaceutical application of the C60‐bound polymer micelle to cancer photodynamic therapy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011. 相似文献
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